WO2022065475A1 - Treatment agent for acrylic resin fibers, and acrylic resin fiber - Google Patents

Treatment agent for acrylic resin fibers, and acrylic resin fiber Download PDF

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Publication number
WO2022065475A1
WO2022065475A1 PCT/JP2021/035329 JP2021035329W WO2022065475A1 WO 2022065475 A1 WO2022065475 A1 WO 2022065475A1 JP 2021035329 W JP2021035329 W JP 2021035329W WO 2022065475 A1 WO2022065475 A1 WO 2022065475A1
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Prior art keywords
acrylic resin
treatment agent
fiber
carboxylic acid
fibers
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PCT/JP2021/035329
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French (fr)
Japanese (ja)
Inventor
浩気 本田
拓也 松永
啓一郎 大島
Original Assignee
竹本油脂株式会社
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Application filed by 竹本油脂株式会社 filed Critical 竹本油脂株式会社
Priority to CN202180065334.5A priority Critical patent/CN116234956B/en
Publication of WO2022065475A1 publication Critical patent/WO2022065475A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
    • D06M2101/28—Acrylonitrile; Methacrylonitrile

Definitions

  • the present invention relates to a treatment agent for acrylic resin fibers and acrylic resin fibers.
  • carbon fiber is produced by a spinning process of spinning an acrylic resin or the like, a dry densification step of drying and densifying the spun fiber, and a drawing of the dried and densified fiber to produce a carbon fiber precursor which is a synthetic fiber. It is produced by performing a stretching step, a flame-resistant treatment step of making the carbon fiber precursor flame-resistant, and a carbonization treatment step of carbonizing the flame-resistant fiber.
  • a treatment agent for synthetic fibers may be used in order to suppress fluff in the synthetic fiber manufacturing process.
  • Patent Document 1 discloses an acrylic fiber oil agent for producing carbon fiber, which contains a modified silicone having a modifying group containing a nitrogen atom and a branched fatty acid.
  • Patent Document 2 discloses an amino-modified silicone oil composition containing an amino-modified polysiloxane-containing silicone oil, a dicarboxylic acid monoester, an emulsifier, and an aminocarboxylic acid substance.
  • the treatment agent for acrylic resin fibers is required to further improve the performance of the effect of suppressing fluff in the manufacturing process of acrylic resin fibers.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a treatment agent for acrylic resin fibers having a suitable effect of suppressing fluff in the manufacturing process of acrylic resin fibers. Another object of the present invention is to provide an acrylic resin fiber to which the processing agent for the acrylic resin fiber is attached.
  • the gist of the treatment agent for acrylic resin fibers for solving the above problems is that it contains a carboxylic acid compound having an acid value of 60 mgKOH / g or less.
  • the carboxylic acid compound is a compound having an ester bond in the molecule.
  • the carboxylic acid compound is a compound having two or more ester bonds in the molecule.
  • the carboxylic acid compound is a compound having a hydroxy group in the molecule.
  • the acid value of the carboxylic acid compound is preferably 10 to 50 mgKOH / g.
  • the treatment agent for acrylic resin fibers further contains a smoothing agent.
  • the smoothing agent contains amino-modified silicone.
  • the kinematic viscosity of the amino-modified silicone at 25 ° C. is preferably 50 to 7000 mm 2 / s.
  • the treatment agent for acrylic resin fibers preferably further contains a nonionic surfactant.
  • the content ratio of the carboxylic acid compound is 0. It is preferably 1 to 15% by mass.
  • the acrylic resin fibers are carbon fiber precursors.
  • the gist of the acrylic resin fiber for solving the above-mentioned problem is that the above-mentioned treatment agent for acrylic resin fiber is attached.
  • the treatment agent of this embodiment contains a carboxylic acid compound having an acid value of 60 mgKOH / g or less.
  • the fluff suppressing effect of the treatment agent can be improved.
  • carboxylic acid compound examples include, for example, a pentameric condensate of 12-hydroxystearic acid, a hexamer condensate of castor oil fatty acid, a 13-mer condensate of 12-hydroxystearic acid, and 12-hydroxy.
  • Examples thereof include an ester compound obtained by reacting a 15-mol ethylene oxide adduct with adipic acid in a 1: 1 molar ratio, polyoxyethylene (25 mol) lauryl ether acetic acid, and the like.
  • the above carboxylic acid compound may be used alone or in combination of two or more.
  • the carboxylic acid compound may be a commercially available product or may be produced by a known method. When it is produced by a known method, it can be produced, for example, by a dehydration condensation reaction between a hydroxy group and a carboxyl group contained in a raw material.
  • carboxylic acid compound may form a salt with other basic components such as amines and metals in the treatment agent.
  • the acid value of the carboxylic acid compound is preferably 10 to 50 mgKOH / g.
  • the fluff suppressing effect of the treatment agent can be further improved.
  • the acid value of the carboxylic acid compound can be measured according to JIS K0070.
  • the carboxylic acid compound is a compound having an ester bond in the molecule.
  • the number of ester bonds in the molecule of the carboxylic acid compound is not particularly limited, and for example, it is preferable to have two or more ester bonds in the molecule.
  • the number of ester bonds can be calculated by the following formula.
  • the saponification value can be measured according to JIS K0070.
  • carboxylic acid compound is preferably a compound having a hydroxy group in the molecule.
  • the treatment agent of the present embodiment preferably contains a smoothing agent.
  • Examples of the smoothing agent include silicone, ester and the like.
  • the silicone used as a smoothing agent is not particularly limited, and is, for example, dimethyl silicone, phenyl-modified silicone, amino-modified silicone, amide-modified silicone, polyether-modified silicone, aminopolyether-modified silicone, alkyl-modified silicone, and alkyl-aralkyl-modified. Examples thereof include silicone, alkyl polyether-modified silicone, ester-modified silicone, epoxy-modified silicone, carbinol-modified silicone, and mercapto-modified silicone.
  • the ester used as a smoothing agent is not particularly limited, and examples thereof include (1) aliphatic monoalcohols and aliphatic monocarboxylic acids such as octyl palmitate, oleyl laurate, oleyl oleate, and isotetracosyl oleate. Ester compounds of (2) 1,6-hexanediol didecanate, glycerin triolate, trimethyl propantrilaurate, pentaerythritol tetraoctanate and other esters of aliphatic polyvalent alcohols and aliphatic monocarboxylic acids.
  • Ester compounds of aliphatic monoalcohols and aliphatic polyvalent carboxylic acids such as diorail azelate, diorail thiodipropionate, diisocetyl thiodipropionate, diisostearyl thiodipropionate, (4).
  • Ester compounds of aromatic monoalcohol and aliphatic monocarboxylic acid such as benzyl oleate and benzyl laurate
  • aromatic polyvalent alcohol such as bisphenol A dilaurate and dilaurate of alkylene oxide adduct of bisphenol A.
  • Complete ester compound with aliphatic monocarboxylic acid (6)
  • Complete ester compound of aliphatic monoalcohol and aromatic polyvalent carboxylic acid such as bis2-ethylhexylphthalate, diisostearylisophthalate, trioctyl remeritate, etc.
  • Examples thereof include natural fats and oils such as coconut oil, rapeseed oil, sunflower oil, soybean oil, sunflower oil, sesame oil, fish oil and beef fat.
  • a known smoothing agent or the like used as a treatment agent for synthetic fibers may be used.
  • the smoothing agent include amino-modified silicone having a kinematic viscosity at 25 ° C. of 650 mm 2 / s and an amino equivalent of 1800 g / mol, and a kinematic viscosity at 25 ° C. of 90 mm 2 / s and an amino equivalent of 5000 g / mol.
  • An amino-modified silicone an amino-modified silicone having a kinematic viscosity at 25 ° C. of 4500 mm 2 / s and an amino equivalent of 1200 g / mol
  • the smoothing agent preferably contains a modified silicone, and more preferably contains an amino-modified silicone. Further, the kinematic viscosity of the amino-modified silicone at 25 ° C. is preferably 50 to 7000 mm 2 / s.
  • the smoothing agent may be used alone or in combination of two or more.
  • the treatment agent of the present embodiment preferably contains a nonionic surfactant.
  • the nonionic surfactant contained in the treatment agent of the present embodiment is not particularly limited, and is, for example, an alcohol or a carboxylic acid to which an alkylene oxide is added, an ester compound of a carboxylic acid and a polyhydric alcohol, and the like.
  • examples thereof include an ether ester compound obtained by adding an alkylene oxide to an ester compound of a carboxylic acid and a polyhydric alcohol.
  • alcohols used as raw materials for nonionic surfactants include (1) methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, and tetradeca.
  • Branched alkenyl alcohols such as senol and isooctadecenol, (5) cyclic alkyl alcohols such as cyclopentanol and cyclohexanol, (6) phenols, nonylphenols, benzyl alcohols, monostyrene phenols, distyrene phenols, tristyrenes.
  • cyclic alkyl alcohols such as cyclopentanol and cyclohexanol
  • phenols nonylphenols
  • benzyl alcohols monostyrene phenols
  • distyrene phenols tristyrenes.
  • aromatic alcohols such as phenol chemicals.
  • carboxylic acids used as raw materials for nonionic surfactants include (1) octyl acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, and hexadecanoic acid.
  • Linear alkylcarboxylic acids such as heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, docosanoic acid, (2) 2-ethylhexanoic acid, isododecanoic acid, isotridecanic acid, isotetradecanoic acid, isohexadecanoic acid, isooctadecane.
  • Examples thereof include branched alkyl carboxylic acids such as acids, linear alkenyl carboxylic acids such as (3) octadecenoic acid, octadecadienoic acid and octadecatorienic acid, and (4) aromatic carboxylic acids such as benzoic acid.
  • alkylene oxide used as a raw material for the nonionic surfactant examples include ethylene oxide and propylene oxide.
  • the number of moles of alkylene oxide added is appropriately set, but is preferably 0.1 to 60 mol, more preferably 1 to 40 mol, and even more preferably 2 to 30 mol.
  • the number of moles of alkylene oxide added indicates the number of moles of alkylene oxide with respect to 1 mole of alcohols or carboxylic acids in the raw material to be charged.
  • polyhydric alcohol used as a raw material for a nonionic surfactant examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4.
  • nonionic surfactant examples include, for example, 10 mol of ethylene oxide adduct of isodecyl alcohol, 5 mol adduct of ethylene oxide of isooctadecyl alcohol, 5 mol adduct of ethylene oxide of hexyl alcohol, and ethylene of tetradecyl alcohol. Examples thereof include an 8 mol adduct of ethylene oxide.
  • nonionic surfactant one type may be used alone, or two or more types may be used in combination.
  • the content of the carboxylic acid compound, smoothing agent, and nonionic surfactant there is no limit to the content of the carboxylic acid compound, smoothing agent, and nonionic surfactant. Assuming that the total content of the carboxylic acid compound, the smoothing agent, and the nonionic surfactant in the treatment agent is 100% by mass, the content of the carboxylic acid compound is preferably 0.1 to 15% by mass, and 0. It is more preferably 3 to 13% by mass. By specifying such a blending ratio, the fluff suppressing effect of the treatment agent can be further improved.
  • the treatment agent of the first embodiment is attached to the acrylic resin fiber of the present embodiment.
  • the acrylic resin fiber are not particularly limited, and examples thereof include polyacrylic fibers such as polyacrylic acid and modacrylic acid.
  • the acrylic resin fiber a resin-made carbon fiber precursor that becomes a carbon fiber by undergoing a carbonization treatment step described later is preferable.
  • the resin constituting the carbon fiber precursor include acrylic resin.
  • the amount of the treatment agent of the first embodiment attached to the acrylic resin fiber is not particularly limited, but the treatment agent (without solvent) is attached so as to be 0.1 to 2% by mass with respect to the acrylic resin fiber. Is preferable, and it is more preferable to attach the fibers so that the content is 0.3 to 1.2% by mass.
  • Examples of the form of the treatment agent for adhering the treatment agent of the first embodiment to the fiber include an organic solvent solution and an aqueous solution.
  • a method for adhering the treatment agent to the acrylic resin fiber for example, a known method, for example, a dipping method or a spray method, using the treatment agent of the first embodiment and an aqueous solution containing water or a further diluted aqueous solution.
  • a method of adhering by a roller method, a guide lubrication method using a measuring pump, or the like can be applied.
  • the method for producing carbon fiber goes through the following steps 1 to 3.
  • Step 1 A silk-reeling process in which the treatment agent of the first embodiment is attached to an acrylic resin fiber to make a silk reel.
  • Step 2 A flame-resistant treatment step of converting the acrylic resin fiber obtained in the above step 1 into a flame-resistant fiber in an oxidizing atmosphere at 200 to 300 ° C, preferably 230 to 270 ° C.
  • Step 3 A carbonization treatment step in which the flame-resistant fiber obtained in the above step 2 is further carbonized in an inert atmosphere at 300 to 2000 ° C, preferably 300 to 1300 ° C.
  • the yarn-making step further includes a wet spinning step in which the resin is dissolved in a solvent and spun, a dry densification step in which the wet-spun acrylic resin fiber is dried and densified, and a drawing in which the dry and densified acrylic resin fiber is stretched. It is preferable to have a process.
  • the temperature of the drying and densifying step is not particularly limited, but it is preferable to heat the acrylic resin fiber that has undergone the wet spinning step at, for example, 70 to 200 ° C.
  • the timing at which the treatment agent is attached to the acrylic resin fiber is not particularly limited, but it is preferably between the wet spinning step and the dry densification step.
  • the oxidizing atmosphere in the flameproofing treatment step is not particularly limited, and for example, an air atmosphere can be adopted.
  • the inert atmosphere in the carbonization treatment step is not particularly limited, and for example, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or the like can be adopted.
  • the treatment agent of the present embodiment contains a carboxylic acid compound having a predetermined acid value. Therefore, the fluff of the acrylic resin fiber can be suppressed. Further, since the heat resistance of the treatment agent can be improved, the effect of suppressing the fusion of the fibers in the flame-resistant treatment step of the acrylic resin fiber (the effect of suppressing fusion) can be improved.
  • the treatment agent is attached to the acrylic resin fiber between the wet spinning process and the dry densification process. Since it is possible to improve the focusing property of the acrylic resin fiber that has undergone the drying and densifying step and the stretching step, and to improve the focusing property of the flame-resistant fiber that has undergone the flame-resistant treatment step, it is possible to improve the focusing property of the flame-resistant fiber during the carbon fiber manufacturing process. It is possible to suppress the winding of fibers and the generation of fluff. Therefore, the appearance of the carbon fiber can be improved and the strength of the carbon fiber can be improved.
  • the treatment agent is attached to the acrylic resin fiber between the wet spinning step and the dry densification step, but the present invention is not limited to this embodiment.
  • the treatment agent may be attached to the acrylic resin fiber between the drying densification step and the stretching step, or the treatment agent may be attached to the acrylic resin fiber between the stretching step and the flameproofing treatment step.
  • the treatment agent for acrylic resin fibers contains a modified silicone and a nonionic surfactant, but the present invention is not limited to this embodiment. At least one of the modified silicone and the nonionic surfactant may be omitted.
  • the acrylic resin fiber may be a fiber that undergoes a flame resistance treatment step but does not perform a carbonization treatment step.
  • the treatment agent of the first embodiment may be attached to synthetic fibers other than acrylic resin fibers. That is, the treatment agent of the first embodiment does not necessarily have to be for acrylic resin fibers, and may be for synthetic fibers other than acrylic resin fibers.
  • Specific examples of synthetic fibers other than acrylic resin fibers include (1) polyester fibers such as polyethylene terephthalate, polypropylene terephthalate, and polylactic acid ester, (2) polyamide fibers such as nylon 6 and nylon 66, and (3) polyethylene. , Polyethylene-based fibers, (4) cellulose-based fibers, (5) lignin-based fibers, and the like.
  • synthetic fibers that can become carbon fibers through the carbonization treatment step for example, fibers made of resins such as polyethylene resin, phenol resin, cellulose resin, lignin resin, and pitch are preferable.
  • the treatment agent or aqueous liquid of the present embodiment includes stabilizers, antistatic agents, antistatic agents, binders, etc. for maintaining the quality of the treatment agent or aqueous liquid, as long as the effects of the present invention are not impaired.
  • Ingredients used in ordinary treatment agents such as antioxidants and ultraviolet absorbers or aqueous liquids may be further added.
  • Test Category 1 (Preparation of Acrylic Resin Fiber Treatment Agent) (Example 1) Using each component shown in Table 1, the carboxylic acid compound (A-1) is 5%, the smoothing agent (B-1) is 60%, the smoothing agent (B-6) is 20%, and the nonionic surfactant. (C-1) was added to the beaker so as to have a blending ratio of 15%. These were stirred and mixed well. A 25% aqueous solution of the treatment agent for acrylic resin fibers of Example 1 was prepared by gradually adding ion-exchanged water so that the solid content concentration became 25% while continuing stirring.
  • Examples 2 to 19 and Comparative Examples 1 to 4 The treatment agents for acrylic resin fibers of Examples 2 to 19 and Comparative Examples 1 to 4 were prepared by the same method as in Example 1 using each component shown in Table 1.
  • the type and content of the carboxylic acid compound, the type and content of the smoothing agent, and the type and content of the surfactant in the treatment agent of each example are described in the “(A) Carboxylic acid compound” column of Table 1. As shown in the “(B) smoothing agent” column and the “(C) nonionic surfactant” column, respectively.
  • (Carboxylic acid compound) A-1 12-Hydroxystearic acid pentamer condensate A-2: Himasi oil fatty acid hexamer condensate A-3: 12-Hydroxystearic acid 13-mer condensate A-4: 12-hydroxy Carboxylic acid tetramer condensate A-5: 12-Hydroxystearic acid 30-mer condensate A-6: A 10 mol adduct of ethylene oxide of bisphenol A was reacted with adipic acid in a molar ratio of 3: 4.
  • Ester compound A-7 Ester compound obtained by reacting 15 mol of ethylene oxide adduct of bisphenol A with adipic acid at a molar ratio of 1: 1
  • A-8 Polyoxyethylene (25 mol) Lauryl ether acetate rA-1: Himashi Oil fatty acid rA-2: 12 mol of ethylene oxide adduct of nonylphenol and monoester of succinic acid rA-3: Isostearic acid
  • (Smoothing agent) B-1 Amino-modified silicone having a kinematic viscosity at 25 ° C. of 650 mm 2 / s and an amino equivalent of 1800 g / mol
  • B-2 Amino having a kinematic viscosity at 25 ° C. of 90 mm 2 / s and an amino equivalent of 5000 g / mol
  • Modified Silicone B-3 Amino-modified silicone with a kinematic viscosity at 25 ° C. of 4500 mm 2 / s and an amino equivalent of 1200 g / mol
  • B-4 Amino-modified silicone with a kinematic viscosity at 25 ° C.
  • the acrylic resin was wet-spun. Specifically, a copolymer having an extreme viscosity of 1.80 consisting of 95% by mass of acrylonitrile, 3.5% by mass of methyl acrylate, and 1.5% by mass of methacrylic acid is dissolved in dimethylacetamide (DMAC) to have a polymer concentration. A spinning stock solution having a viscosity of 21.0% by mass and a viscosity at 60 ° C. of 500 poise was prepared. The undiluted spinning solution was discharged into a coagulation bath of a 70% by mass aqueous solution of DMAC kept at a spinning bath temperature of 35 ° C. from a spinning cap having a pore diameter (inner diameter) of 0.075 mm and a hole number of 12,000 at a draft ratio of 0.8.
  • DMAC dimethylacetamide
  • Acrylic fiber strands (raw material fibers) in a water-swelled state were prepared by stretching the coagulated yarn 5 times in a water washing tank at the same time as removing the solvent.
  • the acrylic resin fiber treatment agent prepared in Test Category 1 was lubricated with respect to the acrylic fiber strand so that the amount of solid content adhered was 1% by mass (without solvent).
  • the refueling of the acrylic resin fiber treatment agent was carried out by a dipping method using a 4% ion exchange aqueous solution of the acrylic resin fiber treatment agent.
  • the acrylic fiber strands are dried and densified with a heating roller at 130 ° C., further stretched 1.7 times between the heating rollers at 170 ° C., and then wound around a yarn tube using a winding device. I took it.
  • step 2 the yarn is unwound from the wound acrylic resin fiber, treated in a flame-resistant furnace having a temperature gradient of 230 to 270 ° C. for 1 hour under an air atmosphere, and then wound on a yarn tube.
  • a flame-resistant yarn flame-resistant fiber
  • step 3 the yarn is unwound from the wound flame-resistant yarn, fired in a carbonization furnace having a temperature gradient of 300 to 1300 ° C. in a nitrogen atmosphere, converted into carbon fibers, and then made into a yarn tube. Carbon fiber was obtained by winding.
  • Test category 3 evaluation
  • the presence or absence of fluff of the acrylic resin fiber, the fiber bundling property of the flame-resistant fiber, and the fiber fusion of the flame-resistant fiber were evaluated.
  • the procedure for each test is shown below.
  • step 1 of the test category 2 the number of fluffs per hour measured by the fluff counting device installed immediately before the winding device for winding the acrylic resin fiber was evaluated according to the following criteria. The results are shown in the "fluff" column of Table 1.
  • the present invention also includes the following aspects.
  • a treatment agent for synthetic fibers which comprises a carboxylic acid compound having an acid value of 60 mgKOH / g or less.
  • Appendix 2 The treatment agent for synthetic fibers according to Appendix 1, wherein the carboxylic acid compound is a compound having an ester bond in the molecule.
  • Appendix 3 The treatment agent for synthetic fibers according to Appendix 1 or 2, wherein the carboxylic acid compound is a compound having two or more ester bonds in the molecule.
  • Appendix 7 The treatment agent for synthetic fibers according to Appendix 6, wherein the smoothing agent contains an amino-modified silicone.
  • Appendix 8 The treatment agent for synthetic fibers according to Appendix 7, wherein the amino-modified silicone has a kinematic viscosity of 50 to 7000 mm 2 / s at 25 ° C.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention addresses the problem of suppressing fluffing of acrylic resin fibers. A treatment agent for acrylic resin fibers according to the present invention contains a carboxylic acid compound that has an acid value of 60 mgKOH/g or less.

Description

アクリル樹脂繊維用処理剤、及びアクリル樹脂繊維Acrylic resin fiber treatment agent and acrylic resin fiber
　本発明は、アクリル樹脂繊維用処理剤、及びアクリル樹脂繊維に関する。 The present invention relates to a treatment agent for acrylic resin fibers and acrylic resin fibers.
　例えば、炭素繊維は、アクリル樹脂等を紡糸する紡糸工程、紡糸された繊維を乾燥して緻密化する乾燥緻密化工程、乾燥緻密化した繊維を延伸して合成繊維である炭素繊維前駆体を製造する延伸工程、炭素繊維前駆体を耐炎化する耐炎化処理工程、及び耐炎化繊維を炭素化する炭素化処理工程を行なうことにより製造される。 For example, carbon fiber is produced by a spinning process of spinning an acrylic resin or the like, a dry densification step of drying and densifying the spun fiber, and a drawing of the dried and densified fiber to produce a carbon fiber precursor which is a synthetic fiber. It is produced by performing a stretching step, a flame-resistant treatment step of making the carbon fiber precursor flame-resistant, and a carbonization treatment step of carbonizing the flame-resistant fiber.
　合成繊維には、合成繊維の製造工程において毛羽を抑制するために、合成繊維用処理剤が用いられることがある。 For synthetic fibers, a treatment agent for synthetic fibers may be used in order to suppress fluff in the synthetic fiber manufacturing process.
　特許文献１には、窒素原子を含む変性基を持つ変性シリコーンと分岐脂肪酸を含有する炭素繊維製造用アクリル繊維油剤が開示されている。特許文献２には、アミノ変性ポリシロキサンを含有するシリコーン油剤と、ジカルボン酸のモノエステルと、乳化剤と、アミノカルボン酸物質を含むアミノ変性シリコーン油剤組成物が開示されている。 Patent Document 1 discloses an acrylic fiber oil agent for producing carbon fiber, which contains a modified silicone having a modifying group containing a nitrogen atom and a branched fatty acid. Patent Document 2 discloses an amino-modified silicone oil composition containing an amino-modified polysiloxane-containing silicone oil, a dicarboxylic acid monoester, an emulsifier, and an aminocarboxylic acid substance.
特開２０１１－１８４８４２号公報Japanese Unexamined Patent Publication No. 2011-184842 特開平８－２０９５４３号公報Japanese Unexamined Patent Publication No. 8-209543
　ところで、アクリル樹脂繊維用処理剤には、アクリル樹脂繊維の製造工程における毛羽を抑制する効果のさらなる性能向上が求められている。 By the way, the treatment agent for acrylic resin fibers is required to further improve the performance of the effect of suppressing fluff in the manufacturing process of acrylic resin fibers.
　本発明は、こうした実情に鑑みてなされたものであり、その目的は、アクリル樹脂繊維の製造工程における毛羽の抑制効果が好適に向上したアクリル樹脂繊維用処理剤を提供することにある。また、このアクリル樹脂繊維用処理剤が付着したアクリル樹脂繊維を提供することにある。 The present invention has been made in view of such circumstances, and an object of the present invention is to provide a treatment agent for acrylic resin fibers having a suitable effect of suppressing fluff in the manufacturing process of acrylic resin fibers. Another object of the present invention is to provide an acrylic resin fiber to which the processing agent for the acrylic resin fiber is attached.
　上記課題を解決するためのアクリル樹脂繊維用処理剤は、酸価が６０ｍｇＫＯＨ／ｇ以下のカルボン酸化合物を含有することを要旨とする。 The gist of the treatment agent for acrylic resin fibers for solving the above problems is that it contains a carboxylic acid compound having an acid value of 60 mgKOH / g or less.
　上記アクリル樹脂繊維用処理剤について、前記カルボン酸化合物が、分子中にエステル結合を有する化合物であることが好ましい。 Regarding the treatment agent for acrylic resin fibers, it is preferable that the carboxylic acid compound is a compound having an ester bond in the molecule.
　上記アクリル樹脂繊維用処理剤について、前記カルボン酸化合物が、分子中にエステル結合を２個以上有する化合物であることが好ましい。 Regarding the treatment agent for acrylic resin fibers, it is preferable that the carboxylic acid compound is a compound having two or more ester bonds in the molecule.
　上記アクリル樹脂繊維用処理剤について、前記カルボン酸化合物が、分子中にヒドロキシ基を有する化合物であることが好ましい。 Regarding the treatment agent for acrylic resin fibers, it is preferable that the carboxylic acid compound is a compound having a hydroxy group in the molecule.
　上記アクリル樹脂繊維用処理剤について、前記カルボン酸化合物の酸価が、１０～５０ｍｇＫＯＨ／ｇであることが好ましい。 Regarding the treatment agent for acrylic resin fibers, the acid value of the carboxylic acid compound is preferably 10 to 50 mgKOH / g.
　上記アクリル樹脂繊維用処理剤は、更に、平滑剤を含有することが好ましい。 It is preferable that the treatment agent for acrylic resin fibers further contains a smoothing agent.
　上記アクリル樹脂繊維用処理剤について、前記平滑剤が、アミノ変性シリコーンを含有することが好ましい。 Regarding the treatment agent for acrylic resin fibers, it is preferable that the smoothing agent contains amino-modified silicone.
　上記アクリル樹脂繊維用処理剤について、前記アミノ変性シリコーンの２５℃での動粘度が、５０～７０００ｍｍ２／ｓであることが好ましい。 Regarding the treatment agent for acrylic resin fibers, the kinematic viscosity of the amino-modified silicone at 25 ° C. is preferably 50 to 7000 mm 2 / s.
　上記アクリル樹脂繊維用処理剤は、更に、非イオン界面活性剤を含有することが好ましい。 The treatment agent for acrylic resin fibers preferably further contains a nonionic surfactant.
　その場合、上記アクリル樹脂繊維用処理剤中の前記カルボン酸化合物、前記平滑剤、及び前記非イオン界面活性剤の含有割合の合計を１００質量％とすると、前記カルボン酸化合物の含有割合が０．１～１５質量％であることが好ましい。 In that case, assuming that the total content of the carboxylic acid compound, the smoothing agent, and the nonionic surfactant in the treatment agent for acrylic resin fibers is 100% by mass, the content ratio of the carboxylic acid compound is 0. It is preferably 1 to 15% by mass.
　上記アクリル樹脂繊維用処理剤について、前記アクリル樹脂繊維が、炭素繊維前駆体であることが好ましい。 Regarding the treatment agent for acrylic resin fibers, it is preferable that the acrylic resin fibers are carbon fiber precursors.
　上記課題を解決するためのアクリル樹脂繊維は、上記アクリル樹脂繊維用処理剤が付着していることを要旨とする。 The gist of the acrylic resin fiber for solving the above-mentioned problem is that the above-mentioned treatment agent for acrylic resin fiber is attached.
　本発明によると、アクリル樹脂繊維の毛羽を抑制することができる。 According to the present invention, fluffing of acrylic resin fibers can be suppressed.
　（第１実施形態）
　本発明に係るアクリル樹脂繊維用処理剤（以下、単に処理剤ともいう。）を具体化した第１実施形態について説明する。 (First Embodiment)
A first embodiment embodying a treatment agent for acrylic resin fibers (hereinafter, also simply referred to as a treatment agent) according to the present invention will be described.
　本実施形態の処理剤は、酸価が６０ｍｇＫＯＨ／ｇ以下のカルボン酸化合物を含有する。 The treatment agent of this embodiment contains a carboxylic acid compound having an acid value of 60 mgKOH / g or less.
　上記カルボン酸化合物を含有することにより、処理剤の毛羽抑制効果を向上させることができる。 By containing the above carboxylic acid compound, the fluff suppressing effect of the treatment agent can be improved.
　上記のカルボン酸化合物の具体例としては、例えば、１２－ヒドロキシステアリン酸の５量体縮合物、ヒマシ油脂肪酸の６量体縮合物、１２－ヒドロキシステアリン酸の１３量体縮合物、１２－ヒドロキシステアリン酸の４量体縮合物、１２－ヒドロキシステアリン酸の３０量体縮合物、ビスフェノールＡのエチレンオキサイド１０モル付加物とアジピン酸を３：４のモル比で反応させたエステル化合物、ビスフェノールＡのエチレンオキサイド１５モル付加物とアジピン酸を１：１のモル比で反応させたエステル化合物、ポリオキシエチレン（２５モル）ラウリルエーテル酢酸等が挙げられる。 Specific examples of the above carboxylic acid compound include, for example, a pentameric condensate of 12-hydroxystearic acid, a hexamer condensate of castor oil fatty acid, a 13-mer condensate of 12-hydroxystearic acid, and 12-hydroxy. A tetramer condensate of stearic acid, a 30-mer condensate of 12-hydroxystearic acid, an ester compound obtained by reacting 10 molar additions of ethylene oxide of bisphenol A with adipic acid in a molar ratio of 3: 4, bisphenol A. Examples thereof include an ester compound obtained by reacting a 15-mol ethylene oxide adduct with adipic acid in a 1: 1 molar ratio, polyoxyethylene (25 mol) lauryl ether acetic acid, and the like.
　上記のカルボン酸化合物は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 The above carboxylic acid compound may be used alone or in combination of two or more.
　上記カルボン酸化合物は、市販品であってもよいし、公知の方法により製造したものであってもよい。公知の方法により製造する場合は、例えば、原料物質に含まれるヒドロキシ基とカルボキシル基との脱水縮合反応により製造することができる。 The carboxylic acid compound may be a commercially available product or may be produced by a known method. When it is produced by a known method, it can be produced, for example, by a dehydration condensation reaction between a hydroxy group and a carboxyl group contained in a raw material.
　また、上記カルボン酸化合物は、処理剤中で他のアミンや金属等の塩基性成分と塩を形成していてもよい。 Further, the carboxylic acid compound may form a salt with other basic components such as amines and metals in the treatment agent.
　上記カルボン酸化合物の酸価は、１０～５０ｍｇＫＯＨ／ｇであることが好ましい。 The acid value of the carboxylic acid compound is preferably 10 to 50 mgKOH / g.
　カルボン酸化合物の酸価が上記数値範囲であることにより、処理剤の毛羽抑制効果をより向上させることができる。 When the acid value of the carboxylic acid compound is within the above numerical range, the fluff suppressing effect of the treatment agent can be further improved.
　カルボン酸化合物の酸価は、ＪＩＳＫ００７０に準拠して測定することができる。 The acid value of the carboxylic acid compound can be measured according to JIS K0070.
　また、カルボン酸化合物が、分子中にエステル結合を有する化合物であることが好ましい。 Further, it is preferable that the carboxylic acid compound is a compound having an ester bond in the molecule.
　カルボン酸化合物における分子中のエステル結合の数は特に限定されず、例えば、分子中にエステル結合を２個以上有することが好ましい。 The number of ester bonds in the molecule of the carboxylic acid compound is not particularly limited, and for example, it is preferable to have two or more ester bonds in the molecule.
　エステル結合の数は、下記の式によって算出することができる。 The number of ester bonds can be calculated by the following formula.
　エステル結合の数＝（ケン化価－酸価）／（酸価）
　上記ケン化価は、ＪＩＳＫ００７０に準拠して測定することができる。 Number of ester bonds = (saponification value-acid value) / (acid value)
The saponification value can be measured according to JIS K0070.
　また、カルボン酸化合物は、分子中にヒドロキシ基を有する化合物であることが好ましい。 Further, the carboxylic acid compound is preferably a compound having a hydroxy group in the molecule.
　また、本実施形態の処理剤は、平滑剤を含有することが好ましい。 Further, the treatment agent of the present embodiment preferably contains a smoothing agent.
　平滑剤としては、例えば、シリコーン、エステル等が挙げられる。 Examples of the smoothing agent include silicone, ester and the like.
　平滑剤として使用されるシリコーンとしては、特に制限はなく、例えば、ジメチルシリコーン、フェニル変性シリコーン、アミノ変性シリコーン、アミド変性シリコーン、ポリエーテル変性シリコーン、アミノポリエーテル変性シリコーン、アルキル変性シリコーン、アルキルアラルキル変性シリコーン、アルキルポリエーテル変性シリコーン、エステル変性シリコーン、エポキシ変性シリコーン、カルビノール変性シリコーン、メルカプト変性シリコーン等が挙げられる。 The silicone used as a smoothing agent is not particularly limited, and is, for example, dimethyl silicone, phenyl-modified silicone, amino-modified silicone, amide-modified silicone, polyether-modified silicone, aminopolyether-modified silicone, alkyl-modified silicone, and alkyl-aralkyl-modified. Examples thereof include silicone, alkyl polyether-modified silicone, ester-modified silicone, epoxy-modified silicone, carbinol-modified silicone, and mercapto-modified silicone.
　平滑剤として使用されるエステルとしては、特に制限はなく、例えば、（１）オクチルパルミテート、オレイルラウレート、オレイルオレート、イソテトラコシルオレート等の、脂肪族モノアルコールと脂肪族モノカルボン酸とのエステル化合物、（２）１，６－ヘキサンジオールジデカネート、グリセリントリオレート、トリメチロールプロパントリラウレート、ペンタエリスリトールテトラオクタネート等の、脂肪族多価アルコールと脂肪族モノカルボン酸とのエステル化合物、（３）ジオレイルアゼレート、チオジプロピオン酸ジオレイル、チオジプロピオン酸ジイソセチル、チオジプロピオン酸ジイソステアリル等の、脂肪族モノアルコールと脂肪族多価カルボン酸とのエステル化合物、（４）ベンジルオレート、ベンジルラウレート等の、芳香族モノアルコールと脂肪族モノカルボン酸とのエステル化合物、（５）ビスフェノールＡジラウレート、ビスフェノールＡのアルキレンオキサイド付加物のジラウレート等の、芳香族多価アルコールと脂肪族モノカルボン酸との完全エステル化合物、（６）ビス２－エチルヘキシルフタレート、ジイソステアリルイソフタレート、トリオクチルトリメリテート等の、脂肪族モノアルコールと芳香族多価カルボン酸との完全エステル化合物、（７）ヤシ油、ナタネ油、ヒマワリ油、大豆油、ヒマシ油、ゴマ油、魚油及び牛脂等の天然油脂等が挙げられる。その他、合成繊維用処理剤に採用されている公知の平滑剤等を使用してもよい。 The ester used as a smoothing agent is not particularly limited, and examples thereof include (1) aliphatic monoalcohols and aliphatic monocarboxylic acids such as octyl palmitate, oleyl laurate, oleyl oleate, and isotetracosyl oleate. Ester compounds of (2) 1,6-hexanediol didecanate, glycerin triolate, trimethyl propantrilaurate, pentaerythritol tetraoctanate and other esters of aliphatic polyvalent alcohols and aliphatic monocarboxylic acids. Compounds, (3) Ester compounds of aliphatic monoalcohols and aliphatic polyvalent carboxylic acids such as diorail azelate, diorail thiodipropionate, diisocetyl thiodipropionate, diisostearyl thiodipropionate, (4). ) Ester compounds of aromatic monoalcohol and aliphatic monocarboxylic acid such as benzyl oleate and benzyl laurate, (5) With aromatic polyvalent alcohol such as bisphenol A dilaurate and dilaurate of alkylene oxide adduct of bisphenol A. Complete ester compound with aliphatic monocarboxylic acid, (6) Complete ester compound of aliphatic monoalcohol and aromatic polyvalent carboxylic acid such as bis2-ethylhexylphthalate, diisostearylisophthalate, trioctyl remeritate, etc. , (7) Examples thereof include natural fats and oils such as coconut oil, rapeseed oil, sunflower oil, soybean oil, sunflower oil, sesame oil, fish oil and beef fat. In addition, a known smoothing agent or the like used as a treatment agent for synthetic fibers may be used.
　平滑剤の具体例としては、例えば２５℃における動粘度が６５０ｍｍ２／ｓ、アミノ当量が１８００ｇ／ｍｏｌであるアミノ変性シリコーン、２５℃における動粘度が９０ｍｍ２／ｓ、アミノ当量が５０００ｇ／ｍｏｌであるアミノ変性シリコーン、２５℃における動粘度が４５００ｍｍ２／ｓ、アミノ当量が１２００ｇ／ｍｏｌであるアミノ変性シリコーン、２５℃における動粘度が４０ｍｍ２／ｓ、アミノ当量が１８００ｇ／ｍｏｌであるアミノ変性シリコーン、２５℃における動粘度が８０００ｍｍ２／ｓ、アミノ当量が１０００ｇ／ｍｏｌであるアミノ変性シリコーン、２５℃における動粘度が１７００ｍｍ２／ｓ、シリコーン主鎖／ポリエーテル側鎖＝２０／８０（質量比）、エチレンオキサイド／プロピレンオキサイド＝５０／５０（モル比）のポリエーテル変性シリコーン、２５℃における動粘度が１７０００ｍｍ２／ｓ、エポキシ当量：３８００ｇ／ｍｏｌであるエポキシ変性シリコーン、ビスフェノールＡのエチレンオキサイド２モル付加物のジラウリルエステル等が挙げられる。 Specific examples of the smoothing agent include amino-modified silicone having a kinematic viscosity at 25 ° C. of 650 mm 2 / s and an amino equivalent of 1800 g / mol, and a kinematic viscosity at 25 ° C. of 90 mm 2 / s and an amino equivalent of 5000 g / mol. An amino-modified silicone, an amino-modified silicone having a kinematic viscosity at 25 ° C. of 4500 mm 2 / s and an amino equivalent of 1200 g / mol, an amino-modified silicone having a kinematic viscosity at 25 ° C. of 40 mm 2 / s and an amino equivalent of 1800 g / mol. , Amino-modified silicone with kinematic viscosity at 25 ° C of 8000 mm 2 / s and amino equivalent of 1000 g / mol, kinematic viscosity at 25 ° C of 1700 mm 2 / s, silicone main chain / polyether side chain = 20/80 (mass ratio) ), Ethylene oxide / propylene oxide = 50/50 (molar ratio) polyether-modified silicone, kinematic viscosity at 25 ° C. 17000 mm 2 / s, epoxy equivalent: 3800 g / mol, epoxy-modified silicone, bisphenol A ethylene oxide 2 Examples thereof include dilauryl ester as a molar adduct.
　平滑剤は、変性シリコーンを含有することが好ましく、アミノ変性シリコーンを含有することがより好ましい。さらに、アミノ変性シリコーンの２５℃での動粘度が、５０～７０００ｍｍ２／ｓであることが好ましい。 The smoothing agent preferably contains a modified silicone, and more preferably contains an amino-modified silicone. Further, the kinematic viscosity of the amino-modified silicone at 25 ° C. is preferably 50 to 7000 mm 2 / s.
　平滑剤は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 The smoothing agent may be used alone or in combination of two or more.
　また、本実施形態の処理剤は、非イオン界面活性剤を含有することが好ましい。 Further, the treatment agent of the present embodiment preferably contains a nonionic surfactant.
　本実施形態の処理剤に含有される非イオン界面活性剤としては、特に制限はなく、例えば、アルコール類又はカルボン酸類にアルキレンオキサイドを付加させたもの、カルボン酸類と多価アルコールとのエステル化合物、カルボン酸類と多価アルコールとのエステル化合物にアルキレンオキサイドを付加させたエーテル・エステル化合物等が挙げられる。 The nonionic surfactant contained in the treatment agent of the present embodiment is not particularly limited, and is, for example, an alcohol or a carboxylic acid to which an alkylene oxide is added, an ester compound of a carboxylic acid and a polyhydric alcohol, and the like. Examples thereof include an ether ester compound obtained by adding an alkylene oxide to an ester compound of a carboxylic acid and a polyhydric alcohol.
　非イオン界面活性剤の原料として用いられるアルコール類の具体例としては、例えば、（１）メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、オクタノール、ノナノール、デカノール、ウンデカノール、ドデカノール、トリデカノール、テトラデカノール、ペンタデカノール、ヘキサデカノール、ヘプタデカノール、オクタデカノール、ノナデカノール、エイコサノール、ヘンエイコサノール、ドコサノール、トリコサノール、テトラコサノール、ペンタコサノール、ヘキサコサノール、ヘプタコサノール、オクタコサノール、ノナコサノール、トリアコンタノール等の直鎖アルキルアルコール、（２）イソプロパノール、イソブタノール、イソヘキサノール、２－エチルヘキサノール、イソノナノール、イソデカノール、イソドデカノール、イソトリデカノール、イソテトラデカノール、イソトリアコンタノール、イソヘキサデカノール、イソヘプタデカノール、イソオクタデカノール、イソノナデカノール、イソエイコサノール、イソヘンエイコサノール、イソドコサノール、イソトリコサノール、イソテトラコサノール、イソペンタコサノール、イソヘキサコサノール、イソヘプタコサノール、イソオクタコサノール、イソノナコサノール、イソペンタデカノール等の分岐アルキルアルコール、（３）テトラデセノール、ヘキサデセノール、ヘプタデセノール、オクタデセノール、ノナデセノール等の直鎖アルケニルアルコール、（４）イソヘキサデセノール、イソオクタデセノール等の分岐アルケニルアルコール、（５）シクロペンタノール、シクロヘキサノール等の環状アルキルアルコール、（６）フェノール、ノニルフェノール、ベンジルアルコール、モノスチレン化フェノール、ジスチレン化フェノール、トリスチレン化フェノール等の芳香族系アルコール等が挙げられる。 Specific examples of alcohols used as raw materials for nonionic surfactants include (1) methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, and tetradeca. Nord, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eikosanol, heneicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, octacosanol, nonacosanol, tria Linear alkyl alcohols such as Contanol, (2) Isopropanol, Isobutanol, Isohexanol, 2-Ethylhexanol, Isononanol, Isodecanol, Isoddecanol, Isotridecanol, Isotetradecanol, Isotriacontanol, Isohexa Decanol, Isoheptadecanol, Isooctadecanol, Isononadecanol, Isoeicosanol, Isoheneicosanol, Isodocosanol, Isotricosanol, Isotetracosanol, Isopentacosanol, Isohexa Branched alkyl alcohols such as cosanol, isoheptacosanol, isooctacosanol, isononacosanol, isopentadecanol, (3) linear alkenyl alcohols such as tetradecenol, hexadecenol, heptadecenol, octadecenol, nonadesenol, (4) isohexadeno. Branched alkenyl alcohols such as senol and isooctadecenol, (5) cyclic alkyl alcohols such as cyclopentanol and cyclohexanol, (6) phenols, nonylphenols, benzyl alcohols, monostyrene phenols, distyrene phenols, tristyrenes. Examples include aromatic alcohols such as phenol chemicals.
　非イオン界面活性剤の原料として用いられるカルボン酸類の具体例としては、例えば、（１）オクチル酸、ノナン酸、デカン酸、ウンデカン酸、ドデカン酸、トリデカン酸、テトラデカン酸、ペンタデカン酸、ヘキサデカン酸、ヘプタデカン酸、オクタデカン酸、ノナデカン酸、エイコサン酸、ヘンエイコサン酸、ドコサン酸等の直鎖アルキルカルボン酸、（２）２－エチルヘキサン酸、イソドデカン酸、イソトリデカン酸、イソテトラデカン酸、イソヘキサデカン酸、イソオクタデカン酸等の分岐アルキルカルボン酸、（３）オクタデセン酸、オクタデカジエン酸、オクタデカトリエン酸等の直鎖アルケニルカルボン酸、（４）安息香酸等の芳香族系カルボン酸等が挙げられる。 Specific examples of carboxylic acids used as raw materials for nonionic surfactants include (1) octyl acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, and hexadecanoic acid. Linear alkylcarboxylic acids such as heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, docosanoic acid, (2) 2-ethylhexanoic acid, isododecanoic acid, isotridecanic acid, isotetradecanoic acid, isohexadecanoic acid, isooctadecane. Examples thereof include branched alkyl carboxylic acids such as acids, linear alkenyl carboxylic acids such as (3) octadecenoic acid, octadecadienoic acid and octadecatorienic acid, and (4) aromatic carboxylic acids such as benzoic acid.
　非イオン界面活性剤の原料として用いられるアルキレンオキサイドの具体例としては、例えばエチレンオキサイド、プロピレンオキサイド等が挙げられる。アルキレンオキサイドの付加モル数は、適宜設定されるが、好ましくは０．１～６０モル、より好ましくは１～４０モル、さらに好ましくは２～３０モルである。なお、アルキレンオキサイドの付加モル数は、仕込み原料中におけるアルコール類又はカルボン酸類１モルに対するアルキレンオキサイドのモル数を示す。 Specific examples of the alkylene oxide used as a raw material for the nonionic surfactant include ethylene oxide and propylene oxide. The number of moles of alkylene oxide added is appropriately set, but is preferably 0.1 to 60 mol, more preferably 1 to 40 mol, and even more preferably 2 to 30 mol. The number of moles of alkylene oxide added indicates the number of moles of alkylene oxide with respect to 1 mole of alcohols or carboxylic acids in the raw material to be charged.
　非イオン界面活性剤の原料として用いられる多価アルコールの具体例としては、例えばエチレングリコール、プロピレングリコール、１，３－プロパンジオール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、１，４－ブタンジオール、２－メチル－１，２－プロパンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、２，５－ヘキサンジオール、２－メチル－２，４－ペンタンジオール、２，３－ジメチル－２，３－ブタンジオール、グリセリン、２－メチル－２－ヒドロキシメチル－１，３－プロパンジオール、２－エチル－２－ヒドロキシメチル－１，３－プロパンジオール、トリメチロールプロパン、ソルビタン、ペンタエリスリトール、ソルビトール等が挙げられる。 Specific examples of the polyhydric alcohol used as a raw material for a nonionic surfactant include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4. -Butandiol, 1,4-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 2-methyl-2,4 -Pentanediol, 2,3-dimethyl-2,3-butanediol, glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2-ethyl-2-hydroxymethyl-1,3-propanediol , Trimethylolpropane, sorbitane, pentaerythritol, sorbitol and the like.
　非イオン界面活性剤の具体例としては、例えばイソデシルアルコールのエチレンオキサイド１０モル付加物、イソオクタデシルアルコールのエチレンオキサイド５モル付加物、へキシルアルコールのエチレンオキサイド５モル付加物、テトラデシルアルコールのエチレンオキサイド８モル付加物等が挙げられる。 Specific examples of the nonionic surfactant include, for example, 10 mol of ethylene oxide adduct of isodecyl alcohol, 5 mol adduct of ethylene oxide of isooctadecyl alcohol, 5 mol adduct of ethylene oxide of hexyl alcohol, and ethylene of tetradecyl alcohol. Examples thereof include an 8 mol adduct of ethylene oxide.
　非イオン界面活性剤は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 As the nonionic surfactant, one type may be used alone, or two or more types may be used in combination.
　上記カルボン酸化合物、平滑剤、非イオン界面活性剤の含有量に制限はない。処理剤中のカルボン酸化合物、平滑剤、非イオン界面活性剤の含有割合の合計を１００質量％とすると、カルボン酸化合物の含有割合が０．１～１５質量％であることが好ましく、０．３～１３質量％であることがより好ましい。かかる配合割合に規定することにより、処理剤の毛羽抑制効果をより向上させることができる。 There is no limit to the content of the carboxylic acid compound, smoothing agent, and nonionic surfactant. Assuming that the total content of the carboxylic acid compound, the smoothing agent, and the nonionic surfactant in the treatment agent is 100% by mass, the content of the carboxylic acid compound is preferably 0.1 to 15% by mass, and 0. It is more preferably 3 to 13% by mass. By specifying such a blending ratio, the fluff suppressing effect of the treatment agent can be further improved.
　（第２実施形態）
　本発明に係るアクリル樹脂繊維を具体化した第２実施形態について説明する。本実施形態のアクリル樹脂繊維には、第１実施形態の処理剤が付着している。アクリル樹脂繊維の具体例としては、特に制限はなく、例えばポリアクリル、モダアクリル等のポリアクリル系繊維が挙げられる。アクリル樹脂繊維としては、後述する炭素化処理工程を経ることにより炭素繊維となる樹脂製の炭素繊維前駆体が好ましい。炭素繊維前駆体を構成する樹脂としては、アクリル樹脂を挙げることができる。 (Second Embodiment)
A second embodiment embodying the acrylic resin fiber according to the present invention will be described. The treatment agent of the first embodiment is attached to the acrylic resin fiber of the present embodiment. Specific examples of the acrylic resin fiber are not particularly limited, and examples thereof include polyacrylic fibers such as polyacrylic acid and modacrylic acid. As the acrylic resin fiber, a resin-made carbon fiber precursor that becomes a carbon fiber by undergoing a carbonization treatment step described later is preferable. Examples of the resin constituting the carbon fiber precursor include acrylic resin.
　第１実施形態の処理剤をアクリル樹脂繊維に付着させる量に特に制限はないが、処理剤（溶媒を含まない）をアクリル樹脂繊維に対し０．１～２質量％となるように付着させることが好ましく、０．３～１．２質量％となるように付着させることがより好ましい。 The amount of the treatment agent of the first embodiment attached to the acrylic resin fiber is not particularly limited, but the treatment agent (without solvent) is attached so as to be 0.1 to 2% by mass with respect to the acrylic resin fiber. Is preferable, and it is more preferable to attach the fibers so that the content is 0.3 to 1.2% by mass.
　第１実施形態の処理剤を繊維に付着させる際の処理剤の形態としては、例えば有機溶媒溶液、水性液等が挙げられる。 Examples of the form of the treatment agent for adhering the treatment agent of the first embodiment to the fiber include an organic solvent solution and an aqueous solution.
　処理剤をアクリル樹脂繊維に付着させる方法としては、例えば、第１実施形態の処理剤、及び水を含有する水性液又はさらに希釈した水溶液を用いて、公知の方法、例えば浸漬法、スプレー法、ローラー法、計量ポンプを用いたガイド給油法等によって付着させる方法を適用できる。 As a method for adhering the treatment agent to the acrylic resin fiber, for example, a known method, for example, a dipping method or a spray method, using the treatment agent of the first embodiment and an aqueous solution containing water or a further diluted aqueous solution. A method of adhering by a roller method, a guide lubrication method using a measuring pump, or the like can be applied.
　本発明に係る処理剤、及びこの処理剤が付着したアクリル樹脂繊維を用いた炭素繊維の製造方法について説明する。 The treatment agent according to the present invention and the method for producing carbon fiber using the acrylic resin fiber to which the treatment agent is attached will be described.
　炭素繊維の製造方法は、下記の工程１～３を経ることが好ましい。 It is preferable that the method for producing carbon fiber goes through the following steps 1 to 3.
　工程１：第１実施形態の処理剤をアクリル樹脂繊維に付着させて製糸する製糸工程。 Step 1: A silk-reeling process in which the treatment agent of the first embodiment is attached to an acrylic resin fiber to make a silk reel.
　工程２：前記工程１で得られたアクリル樹脂繊維を２００～３００℃、好ましくは２３０～２７０℃の酸化性雰囲気中で耐炎化繊維に転換する耐炎化処理工程。 Step 2: A flame-resistant treatment step of converting the acrylic resin fiber obtained in the above step 1 into a flame-resistant fiber in an oxidizing atmosphere at 200 to 300 ° C, preferably 230 to 270 ° C.
　工程３：前記工程２で得られた耐炎化繊維をさらに３００～２０００℃、好ましくは３００～１３００℃の不活性雰囲気中で炭化させる炭素化処理工程。 Step 3: A carbonization treatment step in which the flame-resistant fiber obtained in the above step 2 is further carbonized in an inert atmosphere at 300 to 2000 ° C, preferably 300 to 1300 ° C.
　製糸工程は、さらに、樹脂を溶媒に溶解して紡糸する湿式紡糸工程、湿式紡糸されたアクリル樹脂繊維を乾燥して緻密化する乾燥緻密化工程、及び乾燥緻密化したアクリル樹脂繊維を延伸する延伸工程を有していることが好ましい。 The yarn-making step further includes a wet spinning step in which the resin is dissolved in a solvent and spun, a dry densification step in which the wet-spun acrylic resin fiber is dried and densified, and a drawing in which the dry and densified acrylic resin fiber is stretched. It is preferable to have a process.
　乾燥緻密化工程の温度は特に限定されないが、湿式紡糸工程を経たアクリル樹脂繊維を、例えば、７０～２００℃で加熱することが好ましい。処理剤をアクリル樹脂繊維に付着させるタイミングは特に限定されないが、湿式紡糸工程と乾燥緻密化工程の間であることが好ましい。 The temperature of the drying and densifying step is not particularly limited, but it is preferable to heat the acrylic resin fiber that has undergone the wet spinning step at, for example, 70 to 200 ° C. The timing at which the treatment agent is attached to the acrylic resin fiber is not particularly limited, but it is preferably between the wet spinning step and the dry densification step.
　耐炎化処理工程における酸化性雰囲気は、特に限定されず、例えば、空気雰囲気を採用することができる。 The oxidizing atmosphere in the flameproofing treatment step is not particularly limited, and for example, an air atmosphere can be adopted.
　炭素化処理工程における不活性雰囲気は、特に限定されず、例えば、窒素雰囲気、アルゴン雰囲気、真空雰囲気等を採用することができる。 The inert atmosphere in the carbonization treatment step is not particularly limited, and for example, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or the like can be adopted.
　本実施形態の処理剤、及びアクリル樹脂繊維によれば、以下のような効果を得ることができる。 According to the treatment agent of the present embodiment and the acrylic resin fiber, the following effects can be obtained.
　（１）本実施形態の処理剤は、所定の酸価を有するカルボン酸化合物を含有している。したがって、アクリル樹脂繊維の毛羽を抑制することができる。また、処理剤の耐熱性を向上させることができるため、アクリル樹脂繊維の耐炎化処理工程における繊維同士の融着を抑制する効果（融着抑制効果）を向上させることができる。 (1) The treatment agent of the present embodiment contains a carboxylic acid compound having a predetermined acid value. Therefore, the fluff of the acrylic resin fiber can be suppressed. Further, since the heat resistance of the treatment agent can be improved, the effect of suppressing the fusion of the fibers in the flame-resistant treatment step of the acrylic resin fiber (the effect of suppressing fusion) can be improved.
　（２）湿式紡糸工程と乾燥緻密化工程の間において、処理剤をアクリル樹脂繊維に付着させている。乾燥緻密化工程、及び延伸工程を経たアクリル樹脂繊維の集束性を向上させたり、耐炎化処理工程を経た耐炎化繊維の集束性を向上させたりすることができるため、炭素繊維の製造工程中の繊維の巻き付けや、毛羽の発生を抑制することができる。したがって、炭素繊維の外観を良好にしたり、炭素繊維の強度を向上させたりすることができる。 (2) The treatment agent is attached to the acrylic resin fiber between the wet spinning process and the dry densification process. Since it is possible to improve the focusing property of the acrylic resin fiber that has undergone the drying and densifying step and the stretching step, and to improve the focusing property of the flame-resistant fiber that has undergone the flame-resistant treatment step, it is possible to improve the focusing property of the flame-resistant fiber during the carbon fiber manufacturing process. It is possible to suppress the winding of fibers and the generation of fluff. Therefore, the appearance of the carbon fiber can be improved and the strength of the carbon fiber can be improved.
　上記実施形態は、以下のように変更して実施できる。上記実施形態、及び、以下の変更例は、技術的に矛盾しない範囲で互いに組み合わせて実施できる。 The above embodiment can be changed and implemented as follows. The above embodiment and the following modified examples can be implemented in combination with each other within a technically consistent range.
　・本実施形態では、湿式紡糸工程と乾燥緻密化工程の間において、処理剤をアクリル樹脂繊維に付着させていたが、この態様に限定されない。乾燥緻密化工程と延伸工程の間において処理剤をアクリル樹脂繊維に付着させても良いし、延伸工程と耐炎化処理工程の間において処理剤をアクリル樹脂繊維に付着させても良い。 -In the present embodiment, the treatment agent is attached to the acrylic resin fiber between the wet spinning step and the dry densification step, but the present invention is not limited to this embodiment. The treatment agent may be attached to the acrylic resin fiber between the drying densification step and the stretching step, or the treatment agent may be attached to the acrylic resin fiber between the stretching step and the flameproofing treatment step.
　・本実施形態において、アクリル樹脂繊維用処理剤は、変性シリコーンと非イオン界面活性剤とを含有していたが、この態様に限定されない。変性シリコーンと非イオン界面活性剤の少なくともいずれか一方が省略されていてもよい。 -In the present embodiment, the treatment agent for acrylic resin fibers contains a modified silicone and a nonionic surfactant, but the present invention is not limited to this embodiment. At least one of the modified silicone and the nonionic surfactant may be omitted.
　・本実施形態において、例えば、アクリル樹脂繊維が、耐炎化処理工程を行なうものの、炭素化処理工程までは行わない繊維であってもよい。 -In the present embodiment, for example, the acrylic resin fiber may be a fiber that undergoes a flame resistance treatment step but does not perform a carbonization treatment step.
　・第１実施形態の処理剤は、アクリル樹脂繊維以外の合成繊維に付着させてもよい。すなわち、第１実施形態の処理剤は、必ずしもアクリル樹脂繊維用でなくてもよく、アクリル樹脂繊維以外の合成繊維用であってもよい。アクリル樹脂繊維以外の合成繊維の具体例としては、例えば（１）ポリエチレンテレフタレート、ポリプロピレンテレフタレート、ポリ乳酸エステル等のポリエステル系繊維、（２）ナイロン６、ナイロン６６等のポリアミド系繊維、（３）ポリエチレン、ポリプロピレン等のポリオレフィン系繊維、（４）セルロース系繊維、（５）リグニン系繊維等が挙げられる。中でも、炭素化処理工程を経ることにより炭素繊維となりうる合成繊維、例えば、ポリエチレン樹脂、フェノール樹脂、セルロース樹脂、リグニン樹脂、ピッチ等の樹脂からなる繊維が好ましい。 -The treatment agent of the first embodiment may be attached to synthetic fibers other than acrylic resin fibers. That is, the treatment agent of the first embodiment does not necessarily have to be for acrylic resin fibers, and may be for synthetic fibers other than acrylic resin fibers. Specific examples of synthetic fibers other than acrylic resin fibers include (1) polyester fibers such as polyethylene terephthalate, polypropylene terephthalate, and polylactic acid ester, (2) polyamide fibers such as nylon 6 and nylon 66, and (3) polyethylene. , Polyethylene-based fibers, (4) cellulose-based fibers, (5) lignin-based fibers, and the like. Among them, synthetic fibers that can become carbon fibers through the carbonization treatment step, for example, fibers made of resins such as polyethylene resin, phenol resin, cellulose resin, lignin resin, and pitch are preferable.
　・本実施形態の処理剤又は水性液には、本発明の効果を阻害しない範囲内において、処理剤又は水性液の品質保持のための安定化剤や制電剤、帯電防止剤、つなぎ剤、酸化防止剤、紫外線吸収剤等の通常処理剤又は水性液に用いられる成分をさらに配合してもよい。 -The treatment agent or aqueous liquid of the present embodiment includes stabilizers, antistatic agents, antistatic agents, binders, etc. for maintaining the quality of the treatment agent or aqueous liquid, as long as the effects of the present invention are not impaired. Ingredients used in ordinary treatment agents such as antioxidants and ultraviolet absorbers or aqueous liquids may be further added.
　以下、本発明の構成及び効果をより具体的に説明するために実施例等を挙げるが、本発明がこれらの実施例に限定されるというものではない。尚、以下の実施例及び比較例の説明において、％は質量％を意味する。 Hereinafter, examples and the like will be given to more specifically explain the configuration and effect of the present invention, but the present invention is not limited to these examples. In the following Examples and Comparative Examples,% means mass%.
　試験区分１（アクリル樹脂繊維用処理剤の調製）
　（実施例１）
　表１に示される各成分を使用し、カルボン酸化合物（Ａ－１）が５％、平滑剤（Ｂ－１）が６０％、平滑剤（Ｂ－６）が２０％、非イオン界面活性剤（Ｃ－１）が１５％の配合割合となるようにビーカーに加えた。これらを撹拌してよく混合した。撹拌を続けながら固形分濃度が２５％となるようにイオン交換水を徐々に添加することで実施例１のアクリル樹脂繊維用処理剤の２５％水性液を調製した。 Test Category 1 (Preparation of Acrylic Resin Fiber Treatment Agent)
(Example 1)
Using each component shown in Table 1, the carboxylic acid compound (A-1) is 5%, the smoothing agent (B-1) is 60%, the smoothing agent (B-6) is 20%, and the nonionic surfactant. (C-1) was added to the beaker so as to have a blending ratio of 15%. These were stirred and mixed well. A 25% aqueous solution of the treatment agent for acrylic resin fibers of Example 1 was prepared by gradually adding ion-exchanged water so that the solid content concentration became 25% while continuing stirring.
　（実施例２～１９及び比較例１～４）
　実施例２～１９及び比較例１～４の各アクリル樹脂繊維用処理剤は、表１に示される各成分を使用し、実施例１と同様の方法にて調製した。 (Examples 2 to 19 and Comparative Examples 1 to 4)
The treatment agents for acrylic resin fibers of Examples 2 to 19 and Comparative Examples 1 to 4 were prepared by the same method as in Example 1 using each component shown in Table 1.
　なお、各例の処理剤中におけるカルボン酸化合物の種類と含有量、平滑剤の種類と含有量、及び界面活性剤の種類と含有量は、表１の「（Ａ）カルボン酸化合物」欄、「（Ｂ）平滑剤」欄、及び「（Ｃ）非イオン界面活性剤」欄にそれぞれ示すとおりである。 The type and content of the carboxylic acid compound, the type and content of the smoothing agent, and the type and content of the surfactant in the treatment agent of each example are described in the “(A) Carboxylic acid compound” column of Table 1. As shown in the "(B) smoothing agent" column and the "(C) nonionic surfactant" column, respectively.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１の記号欄に記載するＡ－１～Ａ－８、ｒＡ１～ｒＡ－３、Ｂ－１～Ｂ－８、Ｃ－１～Ｃ－４の各成分の詳細は以下のとおりである。 Details of each component of A-1 to A-8, rA1 to rA-3, B-1 to B-8, and C-1 to C-4 described in the symbol column of Table 1 are as follows.
　（カルボン酸化合物）
　Ａ－１：１２－ヒドロキシステアリン酸の５量体縮合物
　Ａ－２：ヒマシ油脂肪酸の６量体縮合物
　Ａ－３：１２－ヒドロキシステアリン酸の１３量体縮合物
　Ａ－４：１２－ヒドロキシステアリン酸の４量体縮合物
　Ａ－５：１２－ヒドロキシステアリン酸の３０量体縮合物
　Ａ－６：ビスフェノールＡのエチレンオキサイド１０モル付加物とアジピン酸を３：４のモル比で反応させたエステル化合物
　Ａ－７：ビスフェノールＡのエチレンオキサイド１５モル付加物とアジピン酸を１：１のモル比で反応させたエステル化合物
　Ａ－８：ポリオキシエチレン（２５モル）ラウリルエーテル酢酸
　ｒＡ－１：ヒマシ油脂肪酸
　ｒＡ－２：ノニルフェノールのエチレンオキサイド１２モル付加物とコハク酸のモノエステル
　ｒＡ－３：イソステアリン酸
　上記カルボン酸化合物に用いられるカルボン酸化合物の種類、酸価、ケン化価、及び分子中のエステル結合の数について、表２の「（Ａ）カルボン酸化合物」欄、「酸価（ｍｇＫＯＨ／ｇ）」欄、「ケン化価（ｍｇＫＯＨ／ｇ）」欄、及び「分子中のエステル結合の数」欄にそれぞれ示す。 (Carboxylic acid compound)
A-1: 12-Hydroxystearic acid pentamer condensate A-2: Himasi oil fatty acid hexamer condensate A-3: 12-Hydroxystearic acid 13-mer condensate A-4: 12-hydroxy Carboxylic acid tetramer condensate A-5: 12-Hydroxystearic acid 30-mer condensate A-6: A 10 mol adduct of ethylene oxide of bisphenol A was reacted with adipic acid in a molar ratio of 3: 4. Ester compound A-7: Ester compound obtained by reacting 15 mol of ethylene oxide adduct of bisphenol A with adipic acid at a molar ratio of 1: 1 A-8: Polyoxyethylene (25 mol) Lauryl ether acetate rA-1: Himashi Oil fatty acid rA-2: 12 mol of ethylene oxide adduct of nonylphenol and monoester of succinic acid rA-3: Isostearic acid The type, acid value, saponification value, and molecular weight of the carboxylic acid compound used in the above carboxylic acid compound. Regarding the number of ester bonds, Table 2, "(A) Carboxylic acid compound" column, "Acid value (mgKOH / g)" column, "Kenka value (mgKOH / g)" column, and "Ester bond in molecule" Shown in the "Number" column.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　（平滑剤）
　Ｂ－１：２５℃における動粘度が６５０ｍｍ２／ｓ、アミノ当量が１８００ｇ／ｍｏｌであるアミノ変性シリコーン
　Ｂ－２：２５℃における動粘度が９０ｍｍ２／ｓ、アミノ当量が５０００ｇ／ｍｏｌであるアミノ変性シリコーン
　Ｂ－３：２５℃における動粘度が４５００ｍｍ２／ｓ、アミノ当量が１２００ｇ／ｍｏｌであるアミノ変性シリコーン
　Ｂ－４：２５℃における動粘度が４０ｍｍ２／ｓ、アミノ当量が１８００ｇ／ｍｏｌであるアミノ変性シリコーン
　Ｂ－５：２５℃における動粘度が８０００ｍｍ２／ｓ、アミノ当量が１０００ｇ／ｍｏｌであるアミノ変性シリコーン
　Ｂ－６：２５℃における動粘度が１７００ｍｍ２／ｓ、シリコーン主鎖／ポリエーテル側鎖＝２０／８０（質量比）、エチレンオキサイド／プロピレンオキサイド＝５０／５０（モル比）のポリエーテル変性シリコーン
　Ｂ－７：２５℃における動粘度が１７０００ｍｍ２／ｓ、エポキシ当量：３８００ｇ／ｍｏｌであるエポキシ変性シリコーン
　Ｂ－８：ビスフェノールＡのエチレンオキサイド２モル付加物のジラウリルエステル
　（非イオン界面活性剤）
　Ｃ－１：イソデシルアルコールのエチレンオキサイド１０モル付加物
　Ｃ－２：イソオクタデシルアルコールのエチレンオキサイド５モル付加物
　Ｃ－３：へキシルアルコールのエチレンオキサイド５モル付加物
　Ｃ－４：テトラデシルアルコールのエチレンオキサイド８モル付加物
　試験区分２（アクリル樹脂繊維、及び炭素繊維の製造）
　試験区分１で調製したアクリル樹脂繊維用処理剤を用いて、アクリル樹脂繊維、及び炭素繊維を製造した。 (Smoothing agent)
B-1: Amino-modified silicone having a kinematic viscosity at 25 ° C. of 650 mm 2 / s and an amino equivalent of 1800 g / mol B-2: Amino having a kinematic viscosity at 25 ° C. of 90 mm 2 / s and an amino equivalent of 5000 g / mol Modified Silicone B-3: Amino-modified silicone with a kinematic viscosity at 25 ° C. of 4500 mm 2 / s and an amino equivalent of 1200 g / mol B-4: Amino-modified silicone with a kinematic viscosity at 25 ° C. of 40 mm 2 / s and an amino equivalent of 1800 g / mol Amino-modified silicone B-5: 25 ° C. kinematic viscosity is 8000 mm 2 / s, amino equivalent is 1000 g / mol Amino-modified silicone B-6: 25 ° C. kinematic viscosity is 1700 mm 2 / s, silicone main chain / poly Polyether-modified silicone with ether side chain = 20/80 (mass ratio), ethylene oxide / propylene oxide = 50/50 (molar ratio) B-7: The kinematic viscosity at 25 ° C. is 17000 mm 2 / s, epoxy equivalent: 3800 g / Epoxy-modified silicone B-8 which is mol: Dilauryl ester of 2 mol of ethylene oxide adduct of bisphenol A (nonionic surfactant)
C-1: 10 mol adduct of ethylene oxide of isodecyl alcohol C-2: 5 mol adduct of ethylene oxide of isooctadecyl alcohol C-3: 5 mol adduct of ethylene oxide of hexyl alcohol C-4: of tetradecyl alcohol Ethylene oxide 8 mol adduct Test Category 2 (Production of acrylic resin fiber and carbon fiber)
Acrylic resin fibers and carbon fibers were produced using the treatment agent for acrylic resin fibers prepared in Test Category 1.
　まず、工程１として、アクリル樹脂を湿式紡糸した。具体的には、アクリロニトリル９５質量％、アクリル酸メチル３．５質量％、メタクリル酸１．５質量％からなる極限粘度１．８０の共重合体を、ジメチルアセトアミド（ＤＭＡＣ）に溶解してポリマー濃度が２１．０質量％、６０℃における粘度が５００ポイズの紡糸原液を作成した。紡糸原液は、紡浴温度３５℃に保たれたＤＭＡＣの７０質量％水溶液の凝固浴中に孔径（内径）０．０７５ｍｍ、ホール数１２，０００の紡糸口金よりドラフト比０．８で吐出した。 First, as step 1, the acrylic resin was wet-spun. Specifically, a copolymer having an extreme viscosity of 1.80 consisting of 95% by mass of acrylonitrile, 3.5% by mass of methyl acrylate, and 1.5% by mass of methacrylic acid is dissolved in dimethylacetamide (DMAC) to have a polymer concentration. A spinning stock solution having a viscosity of 21.0% by mass and a viscosity at 60 ° C. of 500 poise was prepared. The undiluted spinning solution was discharged into a coagulation bath of a 70% by mass aqueous solution of DMAC kept at a spinning bath temperature of 35 ° C. from a spinning cap having a pore diameter (inner diameter) of 0.075 mm and a hole number of 12,000 at a draft ratio of 0.8.
　凝固糸を水洗槽の中で脱溶媒と同時に５倍に延伸して水膨潤状態のアクリル繊維ストランド（原料繊維）を作成した。このアクリル繊維ストランドに対して、固形分付着量が１質量％（溶媒を含まない）となるように、試験区分１で調製したアクリル樹脂繊維用処理剤を給油した。アクリル樹脂繊維用処理剤の給油は、アクリル樹脂繊維用処理剤の４％イオン交換水溶液を用いた浸漬法により実施した。その後、アクリル繊維ストランドに対して、１３０℃の加熱ローラーで乾燥緻密化処理を行い、更に１７０℃の加熱ローラー間で１．７倍の延伸を施した後に巻き取り装置を用いて糸管に巻き取った。 Acrylic fiber strands (raw material fibers) in a water-swelled state were prepared by stretching the coagulated yarn 5 times in a water washing tank at the same time as removing the solvent. The acrylic resin fiber treatment agent prepared in Test Category 1 was lubricated with respect to the acrylic fiber strand so that the amount of solid content adhered was 1% by mass (without solvent). The refueling of the acrylic resin fiber treatment agent was carried out by a dipping method using a 4% ion exchange aqueous solution of the acrylic resin fiber treatment agent. After that, the acrylic fiber strands are dried and densified with a heating roller at 130 ° C., further stretched 1.7 times between the heating rollers at 170 ° C., and then wound around a yarn tube using a winding device. I took it.
　次に、工程２として、巻き取られたアクリル樹脂繊維から糸を解舒し、２３０～２７０℃の温度勾配を有する耐炎化炉で空気雰囲気下１時間、耐炎化処理した後に糸管に巻き取ることで耐炎化糸（耐炎化繊維）を得た。 Next, as step 2, the yarn is unwound from the wound acrylic resin fiber, treated in a flame-resistant furnace having a temperature gradient of 230 to 270 ° C. for 1 hour under an air atmosphere, and then wound on a yarn tube. As a result, a flame-resistant yarn (flame-resistant fiber) was obtained.
　次に、工程３として、巻き取られた耐炎化糸から糸を解舒し、窒素雰囲気下で３００～１３００℃の温度勾配を有する炭素化炉で焼成して炭素繊維に転換後、糸管に巻き取ることで炭素繊維を得た。 Next, as step 3, the yarn is unwound from the wound flame-resistant yarn, fired in a carbonization furnace having a temperature gradient of 300 to 1300 ° C. in a nitrogen atmosphere, converted into carbon fibers, and then made into a yarn tube. Carbon fiber was obtained by winding.
　試験区分３（評価）
　実施例１～１９及び比較例１～４の処理剤について、アクリル樹脂繊維の毛羽の有無、耐炎化繊維の繊維集束性、及び耐炎化繊維の繊維融着を評価した。各試験の手順について以下に示す。 Test category 3 (evaluation)
With respect to the treatment agents of Examples 1 to 19 and Comparative Examples 1 to 4, the presence or absence of fluff of the acrylic resin fiber, the fiber bundling property of the flame-resistant fiber, and the fiber fusion of the flame-resistant fiber were evaluated. The procedure for each test is shown below.
　（毛羽）
　試験区分２の工程１において、アクリル樹脂繊維を巻き取る巻き取り装置の直前に設置した毛羽計数装置により測定した１時間当たりの毛羽数を以下の基準で評価した。その結果を表１の“毛羽”欄に示す。 (Fluff)
In step 1 of the test category 2, the number of fluffs per hour measured by the fluff counting device installed immediately before the winding device for winding the acrylic resin fiber was evaluated according to the following criteria. The results are shown in the "fluff" column of Table 1.
　・毛羽の評価基準
　◎（良好）：毛羽数が０～５個
　〇（可）：毛羽数が６～１０個
　×（不良）：毛羽数が１１個以上
　（耐炎化集束性）
　試験区分２の工程２において耐炎化処理を行った耐炎化繊維に対して、巻き取り前の耐炎化糸の集束状態を目視で観察して、以下の基準で耐炎化集束性の評価を行った。その結果を表１の“耐炎化集束性”欄に示す。 ・ Evaluation criteria for fluff ◎ (good): 0 to 5 fluffs 〇 (possible): 6 to 10 fluffs × (poor): 11 or more fluffs (flame resistance and focusing)
For the flame-resistant fiber that had been flame-resistant in step 2 of test category 2, the focused state of the flame-resistant yarn before winding was visually observed, and the flame-resistant focusing property was evaluated according to the following criteria. .. The results are shown in the "Flame resistance and focusing property" column of Table 1.
　・耐炎化集束性の評価基準
　◎（良好）：集束しており、トウ幅が一定である場合
　〇（可）：集束しているが、トウ幅が一定ではない場合
　×（不良）：繊維束中に空間があり、集束していない場合
　（耐炎化融着）
　試験区分２の工程２において耐炎化処理を行った耐炎化繊維を長さ１０ｍｍに切断し、ポリオキシエチレン（１０）ラウリルエーテルの水溶液中に分散させた。１０分間撹拌した後、繊維の分散状態を目視し、以下の基準で評価した。その結果を表１の“耐炎化融着”欄に示す。 ・ Evaluation criteria for flame resistance and focusing ◎ (Good): When focused and toe width is constant 〇 (Yes): When focused but toe width is not constant × (Defective): Fiber bundle When there is space inside and it is not focused (flameproof fusion)
The flame-resistant fibers subjected to the flame-resistant treatment in step 2 of Test Category 2 were cut to a length of 10 mm and dispersed in an aqueous solution of polyoxyethylene (10) lauryl ether. After stirring for 10 minutes, the dispersed state of the fibers was visually observed and evaluated according to the following criteria. The results are shown in the "flameproof fusion" column of Table 1.
　・耐炎化融着の評価基準
　◎（良好）：繊維が完全に均一に分散しており、短繊維束が存在しない場合
　〇（可）：繊維が概ね均一に分散しているが、短繊維束が存在している場合
　×（不良）：繊維の分散状態が不均一で、多数の短繊維束が存在している場合
　表１の結果から、本発明によれば、アクリル樹脂繊維用処理剤の耐熱性を向上させて、繊維同士の融着抑制効果を向上させることができる。また、耐炎化繊維の繊維集束性を向上させることができる。また、アクリル樹脂繊維の毛羽の発生を抑制することができる。 ・ Evaluation criteria for flame resistance fusion ◎ (Good): When the fibers are completely uniformly dispersed and there is no short fiber bundle 〇 (Yes): The fibers are dispersed almost uniformly, but the staple fiber bundle × (Defective): When the dispersed state of the fibers is non-uniform and a large number of short fiber bundles are present From the results in Table 1, according to the present invention, the treatment agent for acrylic resin fibers It is possible to improve the heat resistance and improve the effect of suppressing fusion between fibers. In addition, the fiber bundling property of the flame-resistant fiber can be improved. In addition, the generation of fluff on the acrylic resin fiber can be suppressed.
　本発明は以下の態様も包含する。 The present invention also includes the following aspects.
　（付記１）
　酸価が６０ｍｇＫＯＨ／ｇ以下のカルボン酸化合物を含有することを特徴とする合成繊維用処理剤。 (Appendix 1)
A treatment agent for synthetic fibers, which comprises a carboxylic acid compound having an acid value of 60 mgKOH / g or less.
　（付記２）
　前記カルボン酸化合物が、分子中にエステル結合を有する化合物である付記１に記載の合成繊維用処理剤。 (Appendix 2)
The treatment agent for synthetic fibers according to Appendix 1, wherein the carboxylic acid compound is a compound having an ester bond in the molecule.
　（付記３）
　前記カルボン酸化合物が、分子中にエステル結合を２個以上有する化合物である付記１又は２に記載の合成繊維用処理剤。 (Appendix 3)
The treatment agent for synthetic fibers according to Appendix 1 or 2, wherein the carboxylic acid compound is a compound having two or more ester bonds in the molecule.
　（付記４）
　前記カルボン酸化合物が、分子中にヒドロキシ基を有する化合物である付記１～３のいずれか一つに記載の合成繊維用処理剤。 (Appendix 4)
The treatment agent for synthetic fibers according to any one of Supplementary note 1 to 3, wherein the carboxylic acid compound is a compound having a hydroxy group in the molecule.
　（付記５）
　前記カルボン酸化合物の酸価が、１０～５０ｍｇＫＯＨ／ｇである付記１～４のいずれか一つに記載の合成繊維用処理剤。 (Appendix 5)
The treatment agent for synthetic fibers according to any one of Supplementary note 1 to 4, wherein the acid value of the carboxylic acid compound is 10 to 50 mgKOH / g.
　（付記６）
　更に、平滑剤を含有する付記１～５のいずれか一つに記載の合成繊維用処理剤。 (Appendix 6)
Further, the treatment agent for synthetic fibers according to any one of Supplementary note 1 to 5, which contains a smoothing agent.
　（付記７）
　前記平滑剤が、アミノ変性シリコーンを含有する付記６に記載の合成繊維用処理剤。 (Appendix 7)
The treatment agent for synthetic fibers according to Appendix 6, wherein the smoothing agent contains an amino-modified silicone.
　（付記８）
　前記アミノ変性シリコーンの２５℃での動粘度が、５０～７０００ｍｍ２／ｓである付記７に記載の合成繊維用処理剤。 (Appendix 8)
The treatment agent for synthetic fibers according to Appendix 7, wherein the amino-modified silicone has a kinematic viscosity of 50 to 7000 mm 2 / s at 25 ° C.
　（付記９）
　更に、非イオン界面活性剤を含有する付記１～８のいずれか一つに記載の合成繊維用処理剤。 (Appendix 9)
Further, the treatment agent for synthetic fibers according to any one of Supplementary note 1 to 8, which contains a nonionic surfactant.
　（付記１０）
　更に、非イオン界面活性剤を含有し、
　前記カルボン酸化合物、前記平滑剤、及び前記非イオン界面活性剤の含有割合の合計を１００質量％とすると、前記カルボン酸化合物の含有割合が０．１～１５質量％である付記６～８のいずれか一つに記載の合成繊維用処理剤。 (Appendix 10)
In addition, it contains a nonionic surfactant,
If the total content of the carboxylic acid compound, the smoothing agent, and the nonionic surfactant is 100% by mass, the content of the carboxylic acid compound is 0.1 to 15% by mass. The treatment agent for synthetic fibers according to any one.
　（付記１１）
　前記合成繊維が、炭素繊維前駆体である付記１～１０のいずれか一つに記載の合成繊維用処理剤。 (Appendix 11)
The treatment agent for synthetic fibers according to any one of Supplementary note 1 to 10, wherein the synthetic fiber is a carbon fiber precursor.
　（付記１２）
　付記１～１０のいずれか一つに記載の合成繊維用処理剤が付着していることを特徴とする合成繊維。 (Appendix 12)
A synthetic fiber to which the treatment agent for synthetic fiber according to any one of Supplementary note 1 to 10 is attached.

Claims (12)

  1. 　酸価が６０ｍｇＫＯＨ／ｇ以下のカルボン酸化合物を含有することを特徴とするアクリル樹脂繊維用処理剤。 A treatment agent for acrylic resin fibers characterized by containing a carboxylic acid compound having an acid value of 60 mgKOH / g or less.
  2. 　前記カルボン酸化合物が、分子中にエステル結合を有する化合物である請求項１に記載のアクリル樹脂繊維用処理剤。 The treatment agent for acrylic resin fibers according to claim 1, wherein the carboxylic acid compound is a compound having an ester bond in the molecule.
  3. 　前記カルボン酸化合物が、分子中にエステル結合を２個以上有する化合物である請求項１又は２に記載のアクリル樹脂繊維用処理剤。 The treatment agent for acrylic resin fibers according to claim 1 or 2, wherein the carboxylic acid compound is a compound having two or more ester bonds in the molecule.
  4. 　前記カルボン酸化合物が、分子中にヒドロキシ基を有する化合物である請求項１～３のいずれか一項に記載のアクリル樹脂繊維用処理剤。 The treatment agent for acrylic resin fibers according to any one of claims 1 to 3, wherein the carboxylic acid compound is a compound having a hydroxy group in the molecule.
  5. 　前記カルボン酸化合物の酸価が、１０～５０ｍｇＫＯＨ／ｇである請求項１～４のいずれか一項に記載のアクリル樹脂繊維用処理剤。 The treatment agent for acrylic resin fibers according to any one of claims 1 to 4, wherein the acid value of the carboxylic acid compound is 10 to 50 mgKOH / g.
  6. 　更に、平滑剤を含有する請求項１～５のいずれか一項に記載のアクリル樹脂繊維用処理剤。 Further, the treatment agent for acrylic resin fibers according to any one of claims 1 to 5, which contains a smoothing agent.
  7. 　前記平滑剤が、アミノ変性シリコーンを含有する請求項６に記載のアクリル樹脂繊維用処理剤。 The treatment agent for acrylic resin fibers according to claim 6, wherein the smoothing agent contains an amino-modified silicone.
  8. 　前記アミノ変性シリコーンの２５℃での動粘度が、５０～７０００ｍｍ２／ｓである請求項７に記載のアクリル樹脂繊維用処理剤。 The treatment agent for acrylic resin fibers according to claim 7, wherein the amino-modified silicone has a kinematic viscosity of 50 to 7000 mm 2 / s at 25 ° C.
  9. 　更に、非イオン界面活性剤を含有する請求項１～８のいずれか一項に記載のアクリル樹脂繊維用処理剤。 The treatment agent for acrylic resin fibers according to any one of claims 1 to 8, further comprising a nonionic surfactant.
  10. 　更に、非イオン界面活性剤を含有し、
    　前記カルボン酸化合物、前記平滑剤、及び前記非イオン界面活性剤の含有割合の合計を１００質量％とすると、前記カルボン酸化合物の含有割合が０．１～１５質量％である請求項６～８のいずれか一項に記載のアクリル樹脂繊維用処理剤。     In addition, it contains a nonionic surfactant,
    Claims 6 to 8 in which the content ratio of the carboxylic acid compound is 0.1 to 15% by mass, where the total content of the carboxylic acid compound, the smoothing agent, and the nonionic surfactant is 100% by mass. The treatment agent for acrylic resin fibers according to any one of the above.
  11. 　前記アクリル樹脂繊維が、炭素繊維前駆体である請求項１～１０のいずれか一項に記載のアクリル樹脂繊維用処理剤。 The treatment agent for acrylic resin fiber according to any one of claims 1 to 10, wherein the acrylic resin fiber is a carbon fiber precursor.
  12. 　請求項１～１０のいずれか一項に記載のアクリル樹脂繊維用処理剤が付着していることを特徴とするアクリル樹脂繊維。 Acrylic resin fiber to which the treatment agent for acrylic resin fiber according to any one of claims 1 to 10 is attached.
PCT/JP2021/035329 2020-09-28 2021-09-27 Treatment agent for acrylic resin fibers, and acrylic resin fiber WO2022065475A1 (en)

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